Carbon Isotopic Composition Research Articles

Geochemical evaluation of Sarvak oil reservoir using biomarkers, carbon isotope and trace element: A case study from Southwest Iran

The crude oils of the Sarvak reservoir were studied by integrated geochemical, inorganic and isotopic analyses to evaluate the origin, depositional conditions, geological age, thermal maturity of the source rocks and possible facies from which these oils were sourced. This study provides new insights into the Middle-Jurassic age source rock in the Azar Oilfield. This is the first geochemical study in Azar Oilfield where non-biomarker parameters and biomarker parameters were utilized to achieve the objectives. The n-alkane distribution pattern along with their standard ratios, including CPI (0.83–1.03), TAR (0.18–0.29) and isoprenoids (Pr/Ph, 0.52–0.65) as well as pristane/n-C17 versus phytane/n-C18 cross-plot indicate a marine source of the organic matter deposited in an anoxic condition. The sterane parameters such as C27 and C29 are characterized by the predominance of C27ααα-20R steranes (41%–49%) and also depict the algal source of organic matter. The organic input and facies of the source units were also determined by terpanes C29/C30H, Ts/Tm, C35/C34-HH, and DBT/Phen. The relatively high ratio of C29/C30H along with the ratios of Ts/Tm (<0.5) and C35/C34 (>0.8) reflect the carbonate marine facies of the source rocks. Furthermore, the higher values of the homohopane index (>0.1) along with the low ratio of the gammacerane/C30-H (0.06–0.22) as well as the high ratio of V/Ni (>1) further indicate anoxic environments. The dibenzothiophene/phenanthrene ratios of the oil samples (from 2.43 to 3.25) indicate the marine carbonates/marl zone. This genetic classification is also supported by stable carbon isotopic compositions (δ1³C). Most of the maturity-related biomarkers and non-biomarker parameters such as CPI, steranes-C29S/(S + R), ββ/(αα+ββ), moretane to hopane (M29/C30H), pentacyclic terpanes C27Ts/(Ts + Tm), C32-S/(S + R) hopanes, and methyl phenanthrene index agree that the analyzed oils have originated from mature source rocks. Ultimately, this study has demonstrated that analyses of biomarkers and their stable isotope compositions (δ13C and δ34S) complemented with trace element data provide an excellent novel tool for better understanding the basic concepts in petroleum basins and for solving a wide range of problems during petroleum exploration.

Methane Fluxes from a Rich Fen: Relations with the Hydrochemistry and the Dissolved Carbon Isotopic Composition

Methane Fluxes from a Rich Fen: Relations with the Hydrochemistry and the Dissolved Carbon Isotopic Composition

Resolving and correcting for kinetic biases on methane seep paleotemperature using carbonate ∆47/∆48 analysis.

Methane-derived authigenic carbonate often constitutes the sole remaining record of relic methane seeps. The clumped (∆47) and oxygen isotopic composition of seep carbonates often yield inaccurate temperatures, attributed to kinetic isotope effects and modification of seawater isotope composition by hydrate water. Here, we analyzed the dual-clumped isotope (∆47/∆48) composition of authigenic carbonate from a modern methane seep. We demonstrate that aragonite forms closest to isotopic equilibrium such that its ∆47 can directly yield the correct formational temperature, whereas calcite is unambiguously biased by kinetic isotope effects. Numerical models show that the observed bias in the isotopic composition arises from rate-limiting dehydration/dehydroxylation of HCO3- alongside diffusive fractionation, which can be corrected for with analysis of carbonate ∆47/∆48 values. We demonstrate the utility of dual-clumped isotope analysis for studying seep carbonates, as it reveals the origin and magnitude of kinetic biases and can be used to reconstruct paleotemperature and seawater δ18O.

Stable isotope analysis evidences dietary changes in toxodontids (Mammalia, Notoungulata) across the Neogene-Quaternary from Argentina

Toxodontidae was an extinct family of South American notoungulates, widely studied systematically, but not so much from an ecological perspective. This work aims to improve the knowledge about variations in diet and habitats of different representatives of this group in the context of biotic and abiotic events throughout the last 20 My. The tooth enamel carbon isotope composition (δ13C) of 7 genera recorded in 11 localities of Central, West and Northeastern Argentina, from the Early Miocene to the Late Pleistocene, was analyzed. The diet of the toxodontids studied in this work range from mainly C3 resources during the Miocene, mixed C3-C4 in the Pliocene, to a significant consumption of C4 plants during the Pleistocene. Differences in diet during the Late Pleistocene were also recorded, associated with geographic (i.e., Northeastern vs. Central) and temporal (i.e., glacial vs. interglacial periods) variations, evidencing the adaptive capacity of the group under ecological and environmental pressures.

Characteristics, Sources, and Mechanisms of Soil Respiration under Simulated Rainfall in a Native Karst Forest in Southwestern China

Rainfall significantly affects soil respiration rates by altering microbial activity and organic matter decomposition. In karst regions, it also impacts carbonate dissolution and precipitation, further influencing soil CO2 flux. Investigating the mechanism of rainfall’s impact on soil respiration is essential for accurately evaluating and predicting changes in terrestrial ecosystems. However, our understanding of the interaction between rainfall and soil respiration in the extensive karst ecosystems of southwestern China remains limited. This study conducted field-based simulated rainfall experiments to examine variations in soil respiration rates and elucidate the associated control mechanisms through stable carbon isotope composition analysis. Simulated rainfall significantly increased the CO2 release via soil respiration. We observed significant differences in the δ13C value of soil-respired CO2 before and after simulated rainfall. Following the rain, the δ13C of soil-respired CO2 was enriched compared to that before the rain. Through isotope data analysis, we found that the increased soil CO2 emissions were primarily driven by heterotrophic respiration, likely stimulated via changes in soil moisture, affecting microbial growth conditions. Furthermore, the variation in soil moisture affected carbonate dissolution and precipitation, potentially increasing the soil CO2 release after rainfall. In conclusion, these findings expand our understanding of rainfall’s effects on soil respiration in the native karst forests of southwestern China, contributing to the prediction of carbon cycling processes in such ecosystems. The data from this study have significant implications for addressing the release of greenhouse gases in efforts to combat climate change.

Volcanic activity during the Early–Middle Triassic transition in the Sichuan Basin, South China: Duration, evolution and implications

The felsic volcanogenic tuff known as ‘green bean rock’ (GBR) and its carbonates are widely dispersed across the western Yangtze Block. This study investigates the origin, tectonic setting and genesis of GBR, as well as the environmental disruptions evident in carbonates from the western edge of the Yangtze Block. The analyses include mineralogy, whole‐rock geochemistry and the isotopic composition of zircon Hf, carbon and oxygen in GBR samples from the western edge of the Yangtze Block. The geochemical profile of GBR shows enriched LREE, Th and U content, depleted levels of Nb, Ta, Sr, Ba, K, Rb and Ti, and strong‐to‐moderate negative Eu anomalies (δEu = 0.15–0.18). Zircon Hf isotopes exhibit S‐type geochemical affinities with low negative εHf(t) values (−13.3 to −5.7) and TDM2 ages of 1684–2110 Ma. This suggests that the volcanic ashes originate from the magma of an intermediate to felsic composition. X‐ray directionality data show that the most prevalent clay minerals are illite and illite/smectite. Lithium fixed in these minerals is likely to have leached from brine. Early Triassic variances in δ13C profiles are reliable indicators of environmental disturbances, pointing to cycles of devastation and restoration in marine ecosystems, interspersed with extraneous events including volcanic activity. The study posits that volcano eruptions may have prolonged biotic recovery after the end‐Permian mass extinction.

Multiple isotopes (C-S-N-H) and bound biomarkers in asphaltenes: New constraints on the classification and genesis of reservoir bitumens from the northwestern Sichuan Basin, South China

Reservoir bitumens in the northwestern Sichuan basin are significant for elucidating the sources and charging history of oil and gas, given their widespread occurrence in multiple strata in the area and abundant biomarkers. The debate regarding the origin and genesis of these bitumens has persisted for a long time, due to severe biodegradation and the development of multiple sets of high maturity source rocks with few biomarkers for oil-source correlation. To resolve these questions, asphaltenes, which are more resistant to biodegradation than free hydrocarbons, were systematically analyzed with the bulk multi-isotopes (C-S-N-H), bound molecules and the carbon isotopic compositions of bound individual n-alkanes. These characteristics were then compared to those of bulk bitumen and free hydrocarbons, leading to three main conclusions. In most samples, relatively abundant 25-norhopanes and 17-nortricylic terpanes were identified along with n-alkanes in free hydrocarbons, suggesting at least two oil charging events. In the samples having free n-alkanes, the carbon isotopic compositions of asphaltene-bound n-alkanes closely resemble those of corresponding free n-alkanes. Moreover, the bulk C-S-N isotopic compositions of asphaltene also approach those of corresponding bulk bitumen. These results suggest that the source of the oil charges occuring at different times are mostly the same for an individual sample, though different bitumen samples may have distinct sources. Free hydrocarbons, including n-alkanes and biomarkers, may have been produced by the secondary cracking of asphaltenes. Second, the integration of bulk C-S-N isotopic compositions of the asphaltenes and bitumens has enabled the studied samples to be classified into four groups. Source facies is the primary control of the distinct isotopic compositions with other factors like biodegradation, thermal maturity and migration having only minor influence. In combination with biomarkers, the organic matter and sedimentary environment of source rocks could be characterized for each group. A careful comparison of the bulk C-S-N isotopic compositions of asphaltenes and bitumens with those previously reported for source rocks (organic C and S and bulk N isotopes) suggests the main source rocks in the Upper Ediacarian-Lower Cambrian Formations, supporting the conclusions of previous studies. Furthermore, those source rocks in much younger formations, such as the Middle Permian as well as the Middle Devonian Formations, may also have contributed significantly to the widespread reservoir bitumens in the region. These findings highlight the usefulness of bulk C-S-N isotopic composition of asphaltenes for distinguishing oils with complex genesis and large gas exploration potential of the Upper Paleozoic source rocks in the region.

Mussel Culture Activities Facilitate the Export and Burial of Particulate Organic Carbon

The recent expansion of shellfish mariculture could significantly impact the ocean carbon cycle and its associated biogeochemical processes. To understand the source and fate of particulate organic carbon (POC), a summer cruise was conducted from September 8 to 10, 2022, at a mussel farm on Gouqi Island and its adjacent areas located in the East China Sea. Parameters included in situ temperature and salinity, contents of dissolved oxygen (DO), suspended particulate matter (SPM), POC, and chlorophyll a (Chl a), as well as the stable carbon isotopic composition (δ13C) of organic matter in particle and sediment samples, which were analyzed to facilitate a comparative assessment of the areas inside and outside the mussel farm. The POM was much fresher (POC/Chl a &lt; 150) inside the farm with little impact from sediment resuspension (lower SPM content, 11.6 ± 6.6 mg/L), while a significant influence of sediment resuspension was found outside the farm (SPM &gt; 20 mg/L, POC/Chl a &gt; 150). A two end-member mixing model showed that 82.0 ± 6.0% of POC originated from marine algae within the farm, much higher than that outside the farming area (66.1 ± 7.8%). Moreover, elevated DO saturation but relatively low Chl a concentration within the farm suggested continuous algae consumption following potential high productivity. The averaged δ13C values were similar among suspended POC, sinking POC, and sedimentary organic carbon within the farm, implying the fast export and burial of POC. This is likely due to the filter-feeding habits of mussels, who ingest fresh POC and then pack it as fecal pellets that rapidly settle into the sediment. This study sheds light on the distribution and sources of POM inside and outside the mussel farm on Gouqi Island, enhancing our understanding of the marine carbon cycle on shellfish farms and providing insights into the underlying biogeochemical processes.

Stable isotope evidence for resource partitioning in extinct marine carnivores

Living pinnipeds play essential roles in marine ecosystems and display divergent lineage-specific foraging and habitat preferences. The origin of these ecological strategies remains unclear. We analyzed original (n = 22) and published (n = 93) stable carbon (δ13C) and oxygen (δ18O) isotope compositions of tooth enamel from fossil pinnipeds and coeval marine and terrestrial mammals from the late Early Miocene to early Middle Miocene Temblor Formation, the early Middle Miocene Round Mountain Silt Formation at Sharktooth Hill Bonebed, the Middle Miocene of lower levels of the Monterey Formation, and the late Middle Miocene Santa Margarita Formation from the eastern North Pacific Ocean; and original (n = 43) δ13C and δ18O values from the Early Pliocene Yorktown Formation in the western North Atlantic. As expected for aquatic mammals, pinnipeds and control marine mammals had low δ18O variability relative to coeval terrestrial mammals, indicating minimal diagenetic alteration. Among late Early Miocene and Middle Miocene pinnipeds, Allodesmus had lower δ13C values than coeval taxa indicating offshore foraging, in agreement with predictions based on skeletal morphology. However, Allodesmus from the late Middle Miocene Santa Margarita Formation had overlapping δ13C values with co-occurring cetaceans and pinnipeds suggesting preferential nearshore habitat. The stem otariid Pithanotaria had higher enamel δ13C values than co-occurring pinnipeds, indicating nearshore foraging. The stem odobenid Neotherium had intermediate δ13C values supporting foraging between nearshore and offshore predators. Conversely, the stem odobenid cf. Imagotaria had lower enamel δ18O but comparable δ13C values to coexisting pinnipeds, suggesting the exploitation of estuarine resources. At least two ecologically distinct pinniped groups also occurred in the Yorktown Formation. In this unit, the odobenid Ontocetus and some monachinae phocids were predominantly nearshore foragers, with higher enamel δ13C and δ18O values than simultaneously occurring marine mammals. The second group was exclusively composed of phocids, which had comparatively low δ13C and δ18O values, compatible with northward foraging movements along the western North Atlantic coast. The paleoecological profiles of fossils bear strong similarities to the life modes of extant pinniped communities, implying that extant foraging modes appeared early in pinniped evolution and that resource partitioning contributed to their community structure over time.

Hydrological dynamics and manganese mineralization in the wake of the Sturtian glaciation

The Cryogenian Sturtian and Marinoan glaciations stand as the most extreme climate events in Earth history. Intriguingly, large-scale Mn carbonates characterize the nonglacial interlude of this period in South China. The formation mechanism of Mn carbonates and the potential correlation underlying this temporal association remain elusive. Here, we present an integrated petrographic and geochemical study of drill core materials intercepting the Mn-bearing Datangpo Formation. Rare earth element patterns of these Mn carbonates exhibit positive Ce anomalies and a lack of Y anomalies, which differ from those of modern seawater but resemble marine Mn-Fe oxides. These features, combined with negative carbonate carbon isotope compositions (δ13Ccarb as light as −9.9 ‰ VPDB), indicate the presence of oxide precursors and the incorporation of light carbon during Mn-carbonate precipitation. Phosphate oxygen isotope ratios (δ18Op) of HCl-extractable apatite reveal a ∼4 ‰ difference in the average δ18Op between Mn-rich and Mn-poor rocks. We propose that the more positive δ18Op of Mn-rich samples may result from the dominance of phosphate released by reductive dissolution of metal oxides or a heavier oxygen isotope signal of surrounding waters with which isotopic equilibrium has been reached. We further illustrate how marine invasions into coastal anoxic basins could have triggered the formation of Mn oxides and highlight the role of glaciation–deglaciation in the development of giant Mn deposits.

Himalayas is barrier for transportation of light-absorbing particles from South Asia to inner Third Pole

Through a comprehensive investigation into the historical profiles of black carbon derived from ice cores, the spatial distributions of light-absorbing impurities in snowpit samples, and carbon isotopic compositions of black carbon in snowpit samples of the Third Pole, we have identified that due to barriers of the Himalayas and remove of wet deposition, local sources rather than those from seriously the polluted South Asia are main contributors of light-absorbing impurities in the inner part of the Third Pole. Therefore, reducing emissions from residents of the Third Pole themselves is a more effective way of protecting the glaciers of the inner Third Pole in terms of reducing concentrations of light-absorbing particles in the atmosphere and on glaciers.

Compound-Specific Isotope Analysis Provides Direct Evidence for Identifying the Source of Residual Pesticides Diazinon and Procymidone in the Soil-Plant System.

Compound-specific isotope analysis stands as a promising tool for unveiling the behavior of pesticides in agricultural environments. Using the commercial formulations of persistent fungicide procymidone (PRO) and less persistent insecticide diazinon (DIA), respectively, we analyzed the concentration and carbon isotope composition (δ13C) of the residual pesticides through soil incubation experiments in a greenhouse (for 150 days) and lab conditions (for 50-70 days). Our results showed that the magnitude of δ13C variation depends on pesticide specificity, in which PRO in the soil exhibited little variation in δ13C values over the entire incubation times, while DIA demonstrated an increased δ13C value, with the extent of δ13C variability affected by different spiking concentrations, plant presence, and light conditions. Moreover, the pesticides extracted from soils were isotopically overlapped with those from crop lettuce. Ultimately, the isotope composition of pesticides could infer the degradation and translocation processes and might contribute to identifying the source(s) of pesticide formulation in agricultural fields.

Recycled materials and secondary processes controlled the chemical and isotopic compositions of bubbling gases discharged from two adjacent geothermal springs in the Northern Luzon Arc

Gas emissions from hydrothermal systems can serve as indicators of subsurface activity. In addition to gas sources, hydrothermal gas geochemistry is strongly influenced by secondary processes that occur during/after hydrothermal circulation. Here, we observed statistically significant differences in the geochemical characteristics (except for helium isotopes) of bubbling gases discharged from two adjacent vents in the Northern Luzon Arc. Helium (3He/4He = 4.25–7.09 Ra) in both vents was controlled by mixing between mantle and crustal components, where about 74% of helium was contributed by the mantle. Differences in N2/Ar ratios (∼ 300–330) of the two neighboring springs are attributed to subducted materials and seawater mixing (contributing ∼2.5% N2 and Ar), rather than phase separation in the reaction zone. Specifically, Ar was mainly supplied by atmospheric components that dissolved in the percolated seawater with only 8%–9% contributed by the excess radiogenic 40Ar. Excess N2 relative to Ar was mainly supplied by the decomposition of subducted materials (83%–92%) of the South China Sea plate beneath the Philippine Sea Plate. The Lutao gases showed low CO2 concentrations (0.07–22.2 mmol/mol), despite the high 3He/4He ratios indicating a significant contribution of magmatic components. Magmatic CO2 may have been largely consumed by the high Ca Lutao vent fluids via carbonate precipitation in the reaction zone. Alternatively, stable carbon isotope compositions (δ13C) indicate that Lutao CO2 may be supplied by microbial oxidation of alkanes (e.g., CH4 with concentrations of 14.6–173 mmol/mol in the samples), with fractionation factor ΔCO2–CH4 ranging from −15‰ to −25‰ and conversion rates of <10%. Up to 65% of the CO2 in the 2016 samples experienced secondary calcite precipitation in the discharge zone. Our results indicate that recycled subducted materials could potentially affect the geochemical characteristics of gases discharged from arc-volcanic systems. In addition, the influence of secondary processes needs to be considered before tracing the sources of hydrothermal fluids and/or gases, especially in shallow-water hydrothermal systems.

Изотопный состав углерода и кислорода нижнепермских карбонатных пород лосиноостровской свиты (Приполярный Урал, р. Кожым)

The Paleozoic section on the Kozhim River of the Subpolar Urals is the best sequence of the northern Urals. The border of Carboniferous-Permian deposits are observed on the opposite banks of the Kozhim River and are represented by two types of sections: on the right bank — the Kozhym skeletal mound, on the left bank — depression deposits of mixed composition (Losinoostrov Fm.). The article presents the first information on the isotopic composition of carbon and oxygen in the Lower Permian limestones of the Losinoostrov Fm. It is shown that the obtained data on the isotopic composition on the 13C–18O diagram are visually separated into three clusters. The first cluster with the lowest values of 13C (–0.3…1.1 ‰) and 18O (23.5…25.0 ‰) included the most intensively silicified rocks (siliceous bioclastic limestones, secondary silicitolites, siliceous-carbonate-argillaceous mixtolites and siliceous-argillaceous limestone). The third cluster, with the highest values of 13C (3.9…5.1 ‰) and 18O (26.0…26.8 ‰), includes bioclastic and peloid-micritic limestones. In this case, the 13C values correspond to the range of variations in the carbon isotopic composition indicated in review works on the chemostratigraphic correlation of Permian deposits. The second cluster occupies an intermediate position and is characterized by the values of 13C (2.0…2.8 ‰) and 18O (24.3…25.4 ‰). This cluster is predominantly represented by limestones enriched with terrigenous materials. A comparison is made of the isotopic composition of the limestones of the Losinoostrov Formation with the coeval limestones of the Kozhim skeletal mound, which showed higher values of 13C and 18O in the latter.

Stable carbon isotope composition and intrinsic water use efficiency in plants along an altitudinal gradient on the eastern slope of Yulong Snow Mountain, China

BackgroundStable carbon isotope composition (δ13Cp) can be used to estimate the changes in intrinsic water use efficiency (iWUE) in plants, which helps us to better understand plants’ response strategies to climate change. This study focused on the variations in δ13Cp and iWUE for the different life-form plants (i.e., herbs, shrubs, and trees) along an altitudinal gradient (3300, 3600, 3900, 4100, 4300, and 4500 m) on the eastern slope of Yulong Snow Mountain, southeastern margin of the Qinghai-Tibet Plateau. The response mechanisms of δ13Cp and iWUE for different life-form plants to altitude were thoroughly analyzed in this mountain ecosystem.ResultsThe δ13Cp values of plants on the eastern slopes of Yulong Snow Mountain ranged from − 30.4‰ to − 26.55‰, with a mean of − 28.02‰, indicating a dominance of C3 plants. The δ13Cp and iWUE values varied among different life-form plants in the order of herbs > shrubs > trees, particularly in 3600, 3900, and 4300 m. The δ13Cp and iWUE values for herbs and shrubs increased with altitude and were mainly controlled by air temperature. The two parameters for trees exhibited a trend of initial decrease followed by an increase with altitude. Below 3900 m, the δ13Cp and iWUE values decreased with altitude, influenced by soil moisture. However, above 3900 m, the two parameters increased with altitude, mainly regulated by air temperature. In addition, iWUE was positively correlated with leaf P content but negatively correlated with leaf N:P ratio, especially for herbs and trees, suggesting that P plays a key role in modulating iWUE in this region.ConclusionsThe differentiated responses of water availability for different life-form plants to a higher altitudinal gradient are regulated by air temperature, soil moisture, and leaf P content in the Yulong Snow Mountain. These results provide valuable insights into understanding the water–carbon relationships in high-altitude ecosystems.

CO2 in the atmosphere of Mars depleted in 13C

We present here vertically resolved measurements of the carbon isotopic composition of CO2 in the Martian atmosphere between the surface and 50 km of altitude. The results are based on data taken by the ExoMars Trace Gas Orbiter with the NOMAD instrument and have been aggregated to derive an average vertical profile of 13C/12C. We find no seasonal or spatial trends with variabilities beyond the sensitivity of the measurements. For the analysis, we developed a method that allows us to estimate whether the observed variability of isotopic measurements is beyond their intrinsic accuracy, by exploiting ab-initio spectroscopy and the radiometric noise of the instrument. Applying this method to our data, we find that atmospheric CO2 is depleted in 13C compared to the Earth standard by 30‰ to 45‰, in line with previous ground-based measurements values of the atmosphere and in contrast with the average value obtained by Curiosity at the surface (46 ± 4‰). These differences in isotopic signatures of CO2 as measured across the atmosphere and near-surface pose new questions when inferring the evolution and history of carbon on Mars, and suggest that processes such as a strong atmosphere-surface interactions may be fractionating the carbon reservoirs on the planet.

Trophic interactions between common minke whales (Balaenoptera acutorostrata) and their prey during summer in the northern Barents Sea

Global warming is causing rapid change in marine food webs, particularly at northern latitudes where temperatures are increasing most rapidly. In this study, the diet of common minke whales Balaenoptera acutorostrata was assessed both in terms of short-term (morphological analyses of digestive tract contents) and longer-term (tissue chemical markers: fatty acids and stable isotopes) prey use in the northern Barents Sea to see if they are prey shifting. Samples (blubber cores, muscle, and stomach contents) were obtained from 158 common minke whales taken during Norwegian commercial whaling operations during summer over the period 2016–2020. Two prey items, capelin Mallotus villosus and krill (primarily Thysanoessa sp.), dominated the stomach contents in the entire period of investigation, which included sampling both in June and in August, similar to findings from earlier studies. A few gadoids were also observed in the whale stomachs. Lower blubber fatty acid (FA) contents in 2016/2017 as compared with 2018/2019 were observed. This is most likely explained by differences in sampling time (June in 2016/2017 vs August in 2018/2019, i.e., after a longer feeding period during the summer in the latter case). This explanation also fits with the fact that FA profiles of the 2018/2019 whales were more similar to the FA profiles of the potential prey, presumably reflecting the two months longer assimilation time for these whales. Multidimensional mixing models based on carbon and nitrogen isotope composition of the most likely prey groups suggested that the whales ate mostly krill in four of the five sampling years. In 2018 there were indications of a higher proportion of gadoid fish, showing some dietary flexibility. The trophic level of the whales’ feeding, as interpreted from the nitrogen isotope values, was positively correlated with blubber thickness suggesting that fish-eaters tended to assimilate more energy than whales that focused more exclusively on lower trophic prey. The variation suggested by different dietary analyses methods − stomach contents, fatty acids, and stable isotopes – most likely reflects different turnover times, with muscle stable isotopes likely representing several months of dietary integration, while lipid stores are more dynamic and may represent weeks, and stomach contents represent feeding events during the last few hours. The change in diet of minke whales from small pelagic fishes (in the past) to a greater quantity of krill and demersal fish (seen in this study) suggests that the whales are responding to the ongoing borealization of the Barents Sea ecosystem.

High-resolution carbon and oxygen isotopic compositions of cultured brachiopods: Effect of pH, temperature and growth

Brachiopod shells are ubiquitous since the Early Cambrian up to now. As they secrete a shell made of low-magnesium calcite, more resistant to diagenesis than biocarbonates richer in Mg, their geochemical signatures are generally considered a powerful tool for paleo-environmental and paleo-climatic reconstructions. However, gaps in knowledge still remain on the underlying controls of the shell chemistry, in particular at a high spatial resolution. In this study, in situ oxygen and carbon isotope measurements by SIMS (Secondary Ion Mass Spectrometry) were performed in brachiopod shells of the cold-temperate water species Magellania venosa, constituted of a primary and a secondary layer. The individual specimens studied here grew under controlled conditions mimicking the natural environment and in experiments under low-pH (high pCO2) and high-temperature conditions. Transversal carbon and oxygen profiles showed a “brachiopod pattern” typical of extant two-layered brachiopods, with the primary layer depleted in 18O and 13C relative to equilibrium and the secondary layer showing a gradual increasing trend until reaching a near-equilibrium plateau. Overall, shells cultured at low pH were found to have δ18O and δ13C values closer to equilibrium when compared to shells from the control experiment. These near-equilibrium values may reflect a decrease in shell precipitation rate, leading to less kinetic effects, and/or a more rapid kinetics for the equilibration between DIC species and water. By close pairing of seawater δ18O and δ13C to that of shell microstructure, our study enables us to derive layer-specific C and O enrichment factors, which show the extent of pH and temperature effects superimposed on the seawater δ18O and DIC δ13C signal inherited. Finally, we show that during brachiopod shell growth, newly precipitated calcite is added to the calcite already existing, thus empirically validating the conceptual accretionary growth model proposed by Ackerly (1989).

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Winter monsoon brings substantial terrestrial aerosols to Bay of Bengal and adjacent Indian Ocean: Insights from carbon and nitrogen isotopes

It has been currently recognized that air pollutants (e.g., carbon and nitrogen) from South and Southeast Asia have a significant impact on the coastal waters of the northern Indian Ocean. However, the understanding of dynamics and fates of these pollutants in aerosols to the remote ocean through long-distance transportation still needs to be improved. To address this issue, stable isotopic compositions (δ13C, δ15N) of total carbon (TC) and nitrogen (TN) and other geochemical indexes in aerosols are investigated over the Bay of Bengal (BOB) and the adjacent Indian Ocean during the winter monsoon period. The concentrations of TN, TC and aerosol nutrients exhibited a decreasing trend from the northern BOB (N-BOB) to the southern BOB (S-BOB) and Indian Ocean, reflecting the weakening trend of polluted continental influence from the N-BOB to the ocean. The high concentrations of TC (4.28–18.21 μg m−3) in the aerosols of the N-BOB were mainly influenced by the emissions of coal combustion (68 ± 21%), while the high concentrations of TN (0.69–7.31 μg m−3) in the N-BOB were mainly from biofuel/biomass burning (52 ± 31%). In the S-BOB, the lower concentrations of TC (1.42–2.98 μg m−3) and TN (0.38–2.03 μg m−3) mainly originated from the formation of secondary aerosols and the changes in aerosol chemical composition during long-distance transportation from the continent. The primary marine source was responsible for the low TC and TN concentrations over the Indian Ocean. This study quantifies the nitrogen and carbon source shifts from continental anthropogenic activities in the N-BOB to dominant marine and photochemical transformation sources in the remote ocean, quantitatively deepening the understanding of the impact of terrestrial aerosols on the ocean.